Crystals for a semiconductor radiation detector and method for making the crystals

ABSTRACT

A method for a growing solid-state, spectrometer grade II-VI crystal using a high-pressure hydrothermal process including the following steps: positioning seed crystals in a growth zone of a reactor chamber; positioning crystal nutrient material in the nutrient zone of the chamber; filling the reactor with a solvent fluid; heating and pressuring the chamber until at least a portion of the nutrient material dissolves in the solvent and the solvent becomes supercritical in the nutrient zone; transporting supercritical from the nutrient zone to the growth zone, and growing the seed crystals as nutrients from the supercritical fluid deposit on the crystals.

RELATED APPLICATION

This application is a divisional of application Ser. No. 11/082,846filed Mar. 18, 2005, the entirety of which is incorporated by reference.

BACKGROUND OF THE INVENTION

The field of the invention is high grade, II-VI semiconductor crystalgrowth using high-pressure hydrothermal processes and, in particular,growth of large Cadmium Telluride (CdTe) and Cadmium Zinc Telluride(CZT) crystals.

CdTe and CZT crystals have applicability for compact radiationdetectors. CdTe and CZT detectors have been shown to exhibit good energyresolution, especially as compared to scintillator-based detectors.Since they are direct conversion devices, CdTe and CZT detectorseliminate the need for bulky photomultiplier tubes. Furthermore, CdTeand CZT detectors do not require cryogenic cooling as do high-puritygermanium detectors.

CdTe and CZT crystals are conventionally grown by melting CdTe and CZTand allowing the melt to crystallize. Traveling heater systems,horizontal Bridgman, vertical Bridgman and high pressure Bridgmanmethods have been used to grow CdTe and CZT crystals from the melt orfrom the vapor phase. CdTe and CZT crystals grown by such melt and vaporphase processes tend to suffer from high cost and small crystal size. Inaddition, the crystals produced by these melt and vapor phase processestend to have poor electrical and physical characteristics that greatlylimit their sensitivity and application to economical radiationdetectors. There is a long felt need for a robust technique for growinghigh purity, low-cost single CdTe and CZT crystals of a size suitablefor high sensitivity detection at high resolution.

BRIEF DESCRIPTION OF THE INVENTION

A method for making solid-state, spectrometer grade cadmium telluride(CdTe) and cadmium zinc telluride (CZT) crystals has been developed.CdTe and CZT crystals may be grown by a high-pressure hydrothermalprocess that produces large single crystals. The process delivers highcrystal yields at a low cost and with good spectral resolution.

The CdTe and CZT crystals may be applied in gamma ray and x-raydetectors to provide high resolution and improved detector sensitivity.Examples of other uses of the CdTe and CZT crystals include enhancedHand-Held Radioisotope Identification Devices, Area Search Devices andimage arrays for Radiography, digital x-ray detector arrays, andcomputed tomography systems.

The invention may be embodied as a method for a growing solid-state,spectrometer grade II-VI crystals using a high-pressure hydrothermalprocess including the following steps: positioning seed crystals in agrowth zone of a reactor chamber; positioning crystal nutrient materialin the nutrient zone of the chamber; filling the reactor with a solventfluid; heating and pressurizing the chamber until at least a portion ofthe nutrient material dissolves in the solvent and the solvent becomessupercritical; transporting nutrient material dissolved in thesupercritical fluid from the nutrient zone to the growth zone, andgrowing the seed crystals as nutrient material dissolved in thesupercritical fluid deposits onto the crystals.

The invention may also be embodied as a method for growing CadmiumTelluride (CdTe) and Cadmium Zinc Telluride (CZT) crystals comprising:positioning CZT or CdTe seed crystals in a growth zone of a reactorchamber divided by a porous baffle into the growth zone and a nutrientzone; positioning CZT or CdTe nutrient material in the nutrient zone;filling the reactor chamber with a solvent fluid; heating andpressurizing the reactor such that the solvent fluid becomessupercritical; heating the reactor such that the nutrient zone at adifferent temperature than the growth zone; dissolving the nutrientmaterial into the supercritical fluid; transporting the supercriticalfluid with dissolved nutrient through the baffle and to the growth zone,and growing crystals from the seed crystals as the dissolved nutrientsdeposit on the crystals.

Further, the invention may be embodied as a solid-state, spectrometergrade crystal, wherein the crystal is formed by: positioning seedcrystals in a growth zone of a reactor chamber; positioning crystalnutrient material in the nutrient zone of the chamber; filling thereactor with a solvent fluid; heating and pressurizing the chamber untilat least a portion of the nutrient material dissolves in the solvent andthe solvent becomes supercritical; transporting supercritical fluid fromthe nutrient zone to the growth zone, and growing the seed crystals asnutrients from the supercritical fluid deposit onto the crystals.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a zero-stroke-type pressureapparatus with a chamber for growing crystals.

FIG. 2 is a schematic diagram of the chamber for growing CdTe and CZTcrystals by a high-pressure hydrothermal method.

FIG. 3 is a flow chart of an exemplary method for growing thesecrystals.

FIG. 4 is a scanning electron micrograph (SEM) image of spiral growthfeatures on a CdTe (111) seed, indicating high quality crystal growth onscrew dislocations.

DETAILED DESCRIPTION OF THE INVENTION

For direct conversion detection of x-rays or gamma rays, a high quality,wide-bandgap semiconductor comprising high-atomic-number elements isdesired to provide a high cross section for absorption of radiation, alow electrical conductivity for a low background count rate, and a highcarrier mobility and lifetime, for efficient detection of carriers. PureCdTe may be suitable for these purposes, but incorporation ofunintentional impurities and defects may increase the electricalconductivity to an undesirably high value. The conductivity may bereduced by addition of at least one compensatory dopant, but at the costof a reduced carrier mobility. ZnTe may be added to the CdTe, formingCdZnTe (or CZT) order to increase the bandgap and decrease theconductivity. A similar effect may be achieved by incorporation of CdSeor ZnSe, forming Cd_(1-x)Zn_(x)Se_(y)Te_(1-y), where 0≦x, y≦1.

Hydrothermal processes are conventionally used to grow α-quartz crystalscommercially. The term hydrothermal also refers to solvothermalprocesses where the supercritical fluid is a substance other than water,such as ammonia or methanol. These processes provide a highly isothermaland uniform crystal growth environment due to the gas-like viscosity ofthe supercritical fluid solvent in the reactor chamber and theself-convection of the fluid produced by the reactor. Conventionalhydrothermal autoclave systems operate at pressures and temperatures upto about 2 kbar and 400° C., respectively or, with the use ofnickel-based superalloys, up to about 5 kbar and 550° C. When workingwith strongly corrosive solvents, Morey-type autoclaves with a maximumpressure of about 0.5-1 kbar are typically used. Hydrothermal pressurevessel reactors and pressure chambers with enhanced pressure andtemperature capability, up to as high as 80 kbar and 1500° C., aredisclosed in US Patent Application Publications 2003/0141301,2003/0140845, 2004/0134415, and 2006/0177362, all of which are commonlyowned with this application and are incorporated by reference herein intheir entirety.

FIG. 1 illustrates a zero-stroke-type pressure apparatus 10. Theperformance of a high-pressure and high temperature (HP/HT) apparatusmay be characterized by its pressure response, which is defined as thepercent increase in chamber pressure divided by the percent increase inpress force that produces the increased chamber pressure, relative to areference operating condition. As known in the art, a zero strokeapparatus is one in which the pressure response is below 0.2, and, morepreferably below, 0.05.

A zero stroke apparatus is typically easier to control insupercritical-fluid-processing applications than other apparatuses, andis able to capture or contain the pressure generated within the capsulewith little or no tendency to crush it. Although some stroking (e.g., anincrease or decrease in the separation between the punches or anvils)may occur during operation, the extent of stroking is much smaller thanin other designs. Alternatively, a conventional pressure device may beused to pressurize the chamber. A suitable pressure device having achamber, pressure transmission medium, restraint seal and heater isdescribed in published U.S. Patent Application Pub. No. 2003/0140845,published on Jul. 31, 2003, entitled “Improved Pressure Vessel,” andincorporated herein by reference in its entirety.

The zero-stroke apparatus 10 is a HP/HT apparatus comprising a chamber12 for growing crystals (or processing material) in a liquid or solidpressure transmitting medium 13, with at least one electrical insulatorin the apparatus for establishing at least two different electricalheating paths in a heating element and a power system, for independentlycontrolling the temperatures of at least two locations in the cell,wherein the temperature gradient between the seed crystal and the sourcematerial is temporally varying so as to produce an increasing growthrate during at least a portion of the growing process.

The zero-stroke-type pressure apparatus 10 may include opposite steelendcaps 14 that are each surrounded by an annular pyrophyllite bushing16 which, along with gasket 50, electrically insulates opposite anvils18 from the annular die 20. Electrically-conductive element 52establishes an electrical path between anvils 18 and endcaps 14. Anelectrically conductive annulus 22 is interposed about midway betweenthe top and bottom of annular heating element 24 to thermally divide thereaction chamber 12 into an upper section and a lower section. Theheating element 24 may be in the form of a heating tube, or a heatedfoil, ribbon, bar, wire, ring, or combinations thereof. The conductiveannulus 22 has an inner surface in contact with the heating element 24and an outer surface in contact with the die 20.

A main heater power circuit 26 is applied between anvils 18, anddifferential heater power circuit 28 is applied between the die 20 andeither of the anvils 18. Alternatively, one heater circuit 26 can beapplied between the die 20 and first anvil 18 and another circuit 28applied between the die 20 and the second anvil 18. To monitor orcontrol the temperature at the two positions within the chamber, forexample, at the chamber top and bottom, temperature sensors 30 areinserted through the cell components and to desired positions in contactwith or within the chamber, e.g., one sensor at the upper section andanother at the lower section.

The chamber 12 is surrounded by a solid or liquid pressure transmissionmedium 13, such as sodium chloride salt. An annular bushing 15 supportsthe cylindrical heating element 24 and the pressure transmission medium13. The assembly of the bushing 15, heater 24, transmission medium 13and capsule 12 are encased in the die 20 and between the anvils 18.

The chamber 12 may be self-pressurizable up to between 1 atm (about 1bar) and about 80 kbar. For example, the chamber may be is pressurizableup to between about 700 bar and about 80 kbar, including 2 kbar and 5kbar. The chamber 12 may be formed from a deformable material, such ascopper, copper-based alloys, gold, silver, palladium, platinum, iridium,ruthenium, rhodium, osmium, titanium, vanadium, chromium, iron,iron-based alloy, nickel, nickel-based alloy, zirconium, niobium,molybdenum, tantalum, tungsten, rhenium, combinations thereof, and thelike.

FIG. 2 is a schematic diagram of the reactor chamber 12 for growing CdTeand CZT crystals 31. The hydrothermal pressure reactor chamber 12 isdivided into a nutrient zone 32 and a crystal growth zone 33. The zonesare separated by a porous baffle 34. The chamber 12 is filled with asolvent fluid 48 to form a substantially air-free environment that issubjected to high pressure and high temperature (HP/HT) processingconditions. The solvent and HP/HT conditions promote growth of singlecrystal material on seed crystals using dissolved crystal nutrient rawmaterials.

The chamber includes a closed end 37, at least one wall adjoining theclosed end, e.g. a cylindrical wall 36, and a sealed end 35 opposite tothe closed end. The sealed end of the chamber is opened to receivenutrients 40 (e.g., crystal raw materials), solvent fluid 48 and seedcrystals 44. When the sealed end is sealed, the chamber defines a closedHP/HT reactor chamber. The nutrient and a solvent within the chamberbecome a supercritical fluid at high temperatures and high pressures.

As the temperature of the chamber 12 is increased by applying power tothe heating element, the pressure inside the chamber increases due tothe equation of state of the solvent. The chamber deforms outwardslightly due to the internal pressure, but is prevented from largedeformation by forces applied to the pressure transmission medium. Thechamber is fluid impermeable and chemically inert with respect to thereactant and the supercritical fluid under processing conditions. Theprocessing conditions are generally above about 700 bar and 375° Celsius(C.), and more typically above about 2 kilo-bar and 450° C. Preferably,the processing pressures are between 700 bar and 80 kilo-bar (kbar) andthe processing temperatures are between 375° C. and about 1500° C.

The baffle 34 may be a barrier disk with a plurality of through holes.The baffle may be formed of copper, copper-based alloy, gold, silver,palladium, platinum, iridium, ruthenium, rhodium, osmium, titanium,vanadium, chromium, iron, iron-based alloy, nickel, nickel-based alloy,zirconium, niobium, molybdenum, tantalum, tungsten, rhenium, silica,alumina, and combinations thereof. The proportion of open holes to soliddisk in the baffle may be, for example, 0.5% to 30%.

FIG. 3 is a flow chart of a method to grow CdTe and CZT crystals usingan HPHT process. The nutrient zone 32 of the chamber is at leastpartially filled with raw nutrient material 40, e.g., at least one ofpolycrystalline, amorphous, or single crystal Cd, Te, Zn, Se, CdTe,ZnTe, ZnSe, CdSe, CdZnTe, or Cd_(1-x)Zn_(x)Se_(y)Te_(1-y), where0≦x,y≦1, in step 100. The raw nutrient material is preferably of ultrahigh purity, with less than 10 ppm, and even more preferably less than 1ppm, of adventitious impurities. The Cd_(1-x)Zn_(x)Se_(y)Te_(1-y), where0≦x,y≦1, raw material 42 provides nutrients to deposit single-crystalmaterial on the seed crystals 44. The seed crystals are positioned inthe growth zone, such as by suspending the crystals from a rack 46, instep 102. The growth zone may be relatively large, such as up to about ameter in diameter and up to about ten meters in height. Large numbers ofseed crystals may be arranged in a grid array and suspended from one ormore racks in the growth zone. The distance across the grid array ofseed crystals may be several meters.

Chamber 12 is filled with a solvent 48 and a mineralizer. Themineralizer is at least one substance that is added to the solvent toincrease the solubility of the nutrient and crystal material in thesolvent. In one embodiment, the solvent is water and the mineralizer isat least one alkali hydroxide or carbonate. In another embodiment, themineralizer is at least one of a halogen and its reaction products withthe nutrient material, and the solvent is ammonia or an organic such asethylenediamine, methanol or ether.

The solvent 48 and mineralizer may be added to the chamber in severalways. In one embodiment, the mineralizer is added to the chamber, avacuum manifold evacuates the chamber and then the solvent is added tothe chamber from the vapor phase and condensed into the chamber, forexample, by chilling the chamber, in step 104. In another embodiment,the chamber is evacuated by a vacuum manifold and the solvent is addedas a liquid. In yet another embodiment, the solvent is added as a liquidwhile the chamber is open to the atmosphere, then the chamber is closedand evacuated. In still another embodiment, the mineralizer ispre-dissolved in the solvent and added as a liquid to the chamber.Dissolved gases may be removed from the solvent, for example, byboiling, prior to addition to the chamber.

The chamber 12 may be sealed in several ways. In one embodiment, a plugis inserted into one end of the chamber. In another embodiment, a lidwith a fill tube is welded to one end of the chamber prior to finalevacuation of the chamber, then closed off, for example, by welding.

The chamber 12 is positioned in a large high pressure apparatus 10having a heater 24 and a press/punch anvil 18. The solvent, rawmaterials, and mineralizer are placed in the inert, hermetically-sealedbut deformable chamber 12 and encased in a pressure medium 13 in thecavity defined by the die 20 and anvil 18. The heater is capable ofmaintaining the chamber at high and uniform temperatures required forthe processing temperature. The press applies forces to the chamber toprevent deformation and failure due to self-pressurization of the fluidwithin the chamber. An apparatus controller regulates the forces appliedby the press/punch and the temperatures applied by the heater.

The heater circuits 26, 28 maintain the zones 32, 33 in the chamber 12at uniform and elevated temperatures, in step 106. The temperature inthe growth zone may be above 375° C., including for example 450° C. and550° C. In the case where the solubility of the nutrient material in thesupercritical solvent increases with temperature, the temperature in thenutrient zone is maintained at a slightly higher temperature than thetemperature in the growth zone, e.g., above 400° C. For example, thenutrient zone may be maintained 1° C. to 100° C. warmer than the growthzone, and particularly 5° C. to 20° C. warmer. In the case where thesolubility of the nutrient material in the supercritical fluid solventdecreases with temperature, the temperature of the nutrient zone ismaintained at a lower temperature, by about 1 to 100° C., than thegrowth zone. Typically, in the case of solubility with a negativetemperature coefficient, the positions of the growth zone and nutrientzones are reversed with respect to the configuration shown in FIG. 2,with the growth zone in the lower portion of the chamber and thenutrient zone in the upper portion. The heater maintains highly uniformtemperatures in each zone. The heater circuits 26, 28 control thetemperature in the chamber. Power is applied to the heating circuits toheat the chamber from the starting temperature to the operatingtemperature in between about 30 min and about 6 hr, held at theoperating temperature for between about 1 hr and about 2000 hr, andcooled to room temperature in between about 30 min and about 24 hr. Thetemperature difference between the growth zone and the nutrient zone maybe adjusted during the course of the run for improved process control.For example, a temperature difference during the early part of the runthat is reduced in magnitude or even reversed in sign from that employedlater in the run may allow for reduced spontaneous nucleation andimproved crystal quality.

The vapor pressure of the solvent at a given temperature can bedetermined from the equation of state or phase diagram of the solvent.At sufficiently high processing temperatures and pressures the solventfluid and dissolved nutrients becomes a supercritical fluid.

In the case where the solubility of the source material is an increasingfunction of temperature, the nutrient raw material 40 dissolves in thenutrient zone 32 which is at a slightly higher temperature than thegrowth zone, in step 108. The dissolved nutrient is transported to thegrowth zone and supersaturates the growth zone, in step 110. Thedissolved nutrients are transported by convection as the warmer fluid inthe nutrient zone flows towards the cooler growth zone and vice versa.The warmer solvent (supersaturated with nutrients) in the nutrient zonerises and the cooler solvent (in which some of the nutrients haveattached to the seed crystals) in the growth zone sinks because ofdensity differences, causing the reactor to be self stirring. Crystalgrowth on the seed crystal is promoted in the supersaturated growthzone, in step 112.

The dissolved nutrients flow through the baffle 34. The baffle separatesthe growth and nutrient zones, but allows supercritical fluid to flowbetween the zones under HPHT conditions. The baffle also assists inmaintaining the growth and nutrient zones at different temperatures.

The combination of convection and low viscosity enable extremely uniformcrystal growth conditions, so that (for example) several hundred2.5×2.5×15 cm³ crystals can be grown in a single large high pressurechamber and during a single batch process, in step 112. Independentcrystals may be suspended in the growth zone of the chamber. Crystalsseparated by several meters in the chamber will still experience thesame growth rate because the temperature and pressure in the growth zoneis uniform. In addition, individual crystals experience zero thermalstress and may form dislocation-free crystals several cm in diameter.The growing crystals are never in contact with a melt.

FIG. 4 is a scanning electron micrograph (SEM) image of spiral growthfeatures of a CdTe crystal grown on a CdTe(111) seed, indicating highquality crystal growth on screw dislocations. The crystal shown in FIG.4 was grown from a (111)-oriented CdTe seed crystal, approximately 5 mmin diameter and about 1141 μm thick. The seed crystal was placed at thebottom of a copper capsule having a 25 μm thick gold coating on itsinner surface. A gold coated copper baffle, with 5% open area, wasplaced in the middle of the capsule. The source material was 1.07 grams(g) of polycrystalline CdTe that was placed on top of a 40×40 mesh Mowire cloth. The capsule was then filled with 2.17 g of 20M NaOH,corresponding to a fill of about 80% to 85%. The capsule was placedalong with a 0.583 inch diameter steel ring in a filler/sealingassembly. A gold-coated copper plug was then was inserted into the opentop end of the capsule, such that a cold weld was formed between thegold-coated copper capsule and the gold-coated copper plug and the steelring surrounded the plug and provided reinforcement. The capsule wasthen removed from the filler/sealing assembly and inserted in a zerostroke HPHT apparatus. The cell was heated at a rate of about 6.3°C./min until the temperature of the bottom of the capsule wasapproximately 390° C. and the temperature of the top half of the capsulewas approximately 400° C., as measured by type K thermocouples. Thecapsule was held at these temperatures for about 8 hr, then cooled andremoved from the press. Upon opening the capsule, the thickness of theseed was found to have increased by 20.65 μm, corresponding to a growthrate of about 2.6 μm/hr. The surface of the seed crystal was examined byscanning electron microscopy. The scanning electron micrograph (SEM)image of FIG. 4 shows the spiral growth features of the CdTe crystalthat indicates high quality crystal growth on screw dislocations. Withhigher temperatures, e.g., above 450° C. or 550° C., and optimization ofthe process higher crystal growth rates are expected, such as 30-50pm/hr. This particular experiment used a capsule geometry which differsfrom that shown in FIG. 1, in that the seed was on the bottom.Nevertheless, the solubility increased with temperature and the bottomwas cooler than the top. Higher crystal growth rates are expected, suchas 30-50 pm/hr., when the process is used with higher temperatures,e.g., above 500° C.

Despite the very high purity and crystalline quality of CdZnSeTecrystals grown by the present method, the presence of low concentrationsof adventitious impurities and native defects such as vacancies andinterstitials may render unintentionally doped crystals conductive,which is undesirable for many radiation detector applications. Thisundesirable electrical conductivity may be greatly reduced by adding atleast one compensatory dopant to the CdZnSeTe crystals. For example, atleast one of Cl, Ge, Sn, In, B, Al, Ga, Tl, C, Si, Pb, N, P, As, Sb, Bi,F. Br, I, a transition metal, a rare earth metal, or H may beincorporated. Other impurities, for example, Be, Mg, Ca, Sr, Ba, O, orS, may be added to modify the bandgap of the CdZnSeTe crystals. The atleast one dopant or impurity may be introduced as an impurity in thenutrient material or as a component of the solvent or the mineralizer.In the case where the dopant is incorporated into the nutrient material,the nutrient is preferably melted and quenched prior to use so that thedopant is homogenously distributed through the nutrient material. Theconcentration of the at least one dopant or impurity in the CdZnSeTecrystals will typically lie in the range of about 10¹⁵ cm⁻³ to about10²¹ cm⁻³. The addition of dopants such as chlorine (Cl) should enableresistivities above 10¹¹ Ω-cm in the CdTe and CZT crystals. Suchresistivities are considerably higher than has been previouslydemonstrated in CdTe but should be achievable due to the expected highercrystal quality. For example, GaN grown in supercritical ammonia has acarrier concentration lower by 10³-10⁴ than GaN grown in liquid Gadespite similar impurity concentrations.

After the conclusion of the crystal growth run, the reactor is cooledand the chamber is removed from the high pressure apparatus. The chamberis cut open and the crystals removed. The crystals may be washed usingat least one of water, inorganic acids, inorganic bases, organicsolvents, organic acids, and organic bases. The crystals may be sawedinto wafers, cubes, or other shapes by means of a wire saw, annular saw,or other method. The cut surfaces of the sawed crystals may be chosen tohave an orientation within about 10° of the (111), ( 111), (110), (100)crystallographic orientations. After cutting, the crystals may be lappedand polished by methods that are well known in the art. To removeresidual surface damage resulting from sawing, lapping, or polishing,the crystals may be etched in 1% Br₂ in methanol. For incorporation intoa radiation detector device, the crystal surfaces may then be passivatedby treatments such as H₂O₂/NH₄F or plasma oxidation. Au electrodes, witha coplanar grid anode and a solid cathode, may then be deposited byeither electroless or sputter deposition.

The crystal growth process is expected to achieve dramatic reductions inthe concentration of inclusions, grain boundaries, micropipes, andcracks and to demonstrate an electron mobility-lifetime product μτgreater than 1-2×10⁻² cm²/V. Crystals produced with the method disclosedherein may be used to manufacture large-volume gamma and x-ray radiationdetectors and spectrometers with an energy resolution better than 2% at662 keV, which in turn should enable low-cost discrimination betweennaturally occurring radioactive materials (NORM), special nuclearmaterials (SNM), and common medical and industrial radioisotopes in ahand-held detector or in an imaging array. The crystals should also beuseful as components of area search devices or gamma ray imaging arrays.In addition, crystals produced by the inventive method may be useful asdirect conversion x-ray detectors, dual- or multi-energy x-raydetectors, x-ray spectrometers, as components of x-ray imaging arrays,and as components of x-ray computed tomography systems.

The disclosed crystal growth method should yield, for example, 1×1×0.5cm³ CdTe and CZT single crystals with a resistivities greater than 10¹¹Ω-cm and electrical properties implying capability for an energyresolution of 2% at 662 keV and room temperature. It is expected thatCZT crystals grown with the HPHT process disclosed herein will haveresistivities in a range 10⁹ Ω-cm to 10¹¹ Ω-cm. CdTe crystals may alsobe grown with similar resistivities. The crystal size is expected to beincreased to 4 cm³, 16 cm³, 27 cm³, 125 cm³ and larger, with thedisclosed method. The photopeak efficiency in a one cm crystal cubeshould be at least as high as standard material, e.g., 8% at 662 keV. Acrystal having a size of 4 cm³ and format of CdTe or CZT crystals shouldproduce a photopeak count rate of about 14 sec⁻¹ at an exposure level of50 μR/hr of 662 keV gamma rays, per ANSI N42.34 8.1.2, enabling anincrease above background to be detected in 1 sec with less than a 1%probability of error.

A resolution of 2% at 662 keV should allow for ready identification ofeach of the SNM, NORM, medical, and industrial radionuclides in ANSIN42.34 singly or in pairs. The crystal may comprise a portion of atleast one of a gamma radiation detector, a gamma ray spectrometer, anarea search device, a gamma ray imaging array, a direct conversion x-raydetector, a dual- or multi-energy x-ray detector, an x-ray spectrometer,an x-ray imaging array, and an x-ray computed tomography system.

While the invention has been described in connection with what ispresently considered to be the most practical and preferred embodiment,it is to be understood that the invention is not to be limited to thedisclosed embodiment, but on the contrary, is intended to cover variousmodifications and equivalent arrangements included within the spirit andscope of the appended claims.

1. A method for a growing solid-state, spectrometer grade II-VI crystalcomprising: positioning seed crystals in a growth zone of a reactorchamber; positioning crystal nutrient material in the nutrient zone ofthe reactor chamber; filling the reactor chamber with a solvent fluid;heating and pressurizing the chamber until at least a portion of thenutrient material dissolves in the solvent and the solvent becomessupercritical; transporting dissolved nutrient from the nutrient zone tothe growth zone, and growing the seed crystals as nutrients from thesupercritical fluid deposit on the crystals.
 2. The method of claim 1wherein said seed crystals comprise Cd_(1-x)Zn_(x)Se_(y)Te_(1-y), where0≦x,y≦1.
 3. The method of claim 1 wherein in the step of growing theseed crystals a growth zone temperature is at least 450° C. and areactor pressure is at least 2 kbar.
 4. The method of claim 1 wherein inthe step of growing the seed crystals a growth zone temperature is atleast 550° C. or the reactor pressure is at least 5 kbar.
 5. The methodof claim 1 wherein in the step of growing the seed crystals at a growthzone temperature of at least 375° C. and at a reactor pressure at least700 bar.
 6. The method of claim 1 further comprising adding a dopant tothe nutrient material, wherein the dopant is selected from a groupconsisting of Cl, Ge, Sn, In, B, Al, Ga, Tl, C, Si, Pb, N, P, As, Sb,Bi, F, Br, I, Be, Mg, Ca, Sr, Ba, O and S.
 7. The method of claim 1further comprising adding a mineralizer to the solvent wherein themineralizer comprises at least one of alkali hydroxide and carbonate. 8.The method of claim 1 wherein the solvent is at least one of an ammonia,ethylenediamine, methanol and ether.
 9. The method of claim 1 whereinpositioning seed crystals includes positioning a plurality of CadmiumTelluride (CdTe) and Cadmium Zinc Telluride (CZT) seed crystals.
 10. Themethod of claim 1 wherein the reactor chamber is divided by a porousbaffle into the growth zone and the nutrient zone.
 11. The method ofclaim 1 wherein the crystal nutrient material includes at least one ofCZT and CdTe.
 12. The method of claim 1 wherein the step of heating thereactor chamber includes heating the reactor chamber such that thenutrient zone is warmer than the growth zone.
 13. The method of claim 1wherein transporting the dissolved nutrient includes passing thenutrient through a baffle between the nutrient zone and the growth zone.14. A method for a growing solid-state, spectrometer grade II-VI crystalcomprising: positioning seed crystals in a growth zone of a reactorchamber; positioning crystal nutrient material in the nutrient zone ofthe chamber, wherein a baffle separates the nutrient zone from thereactor chamber; filling the reactor chamber with a solvent fluid;heating and pressurizing the reactor chamber until at least a portion ofthe nutrient material dissolves in the solvent and the solvent becomessupercritical; transporting dissolved nutrient from the nutrient zone,through the baffle, to the growth zone, and growing the seed crystals asnutrients from the supercritical fluid deposit on the seed crystals at agrowth zone temperature of at least 375° C. and at a reactor pressure atleast 700 bar.
 15. The method of claim 14 further comprising heating thenutrient zone to a temperature that is at least 5° C. different than thegrowth zone, and the step of transporting the supercritical fluidincludes transporting by convection.
 16. The method of claim 14 whereinthe solvent fluid comprises a mineralizer.
 17. The method of claim 14wherein positioning the seed crystals further comprises suspending theseed crystals in the chamber.
 18. The method of claim 14 whereinpositioning the seed crystals further comprises suspending more than onehundred seed crystals in the chamber.
 19. The method of claim 14 whereinsaid nutrient material comprises Cd_(1-x)Zn_(x)Se_(y)Te_(1-y), where0≦x,y≦1.
 20. The method of claim 14 further comprising adding a dopantto the nutrient material, wherein the dopant is selected from a groupconsisting of Cl, Ge, Sn, In, B, Al, Ga, Tl, C, Si, Pb, N, P, As, Sb,Bi, F, Br, I, Be, Mg, Ca, Sr, Ba, O and S.